beta-naphthyl-amincaryl-rydroxy fatty acids



Patented Jan. 31 1933 WINFEID nnn'rn-ror-r, or LEvnnKuenrich-transmits, Jesus HIIQGEIR, or, oonoenn MULHEIM-ON-TI-IE-RHINE, AND RUDOLF KNOCHE,OF.LEVERKUSENQZI-TEE-=3HI1{E, GERMANY, ASSIGNORS 'rc nnznrnn wenxs, 13-10., or unwyonx, N. Y.,

A coRPoRA'rroN or DELAWARE j cMAPHmnYLAMmoAarL-rriznnoXY F TTY ACIDS MENT- wm: ii

No'Drewing. Application filed February 12, "32 :0, Scriatii'o. 427,933, and in Germany February 13, 1929. p

The present invention relatesto a process of preparing ,B-naphthyl-aminoaryl-hy{ droxy fatty acids and to the new products obtainable thereby, more"particularlyit rlates to compounds of the-probable general formula wherein the benzene nuclei R and R may. be

substituted, NH being attached to R in or metaposition to the hydrony-fatty acid an alkylene group, such as CH 1 H 0 H,

etc.

()ur new products are obtaintable by heating in aqueous solution or suspenslon a com pound of the general formula:

wherein :0 stands for an amino or-a hydroxy group and the. qs stand for nydrogern-ono of which may be substituted by a carbonyllc acic group, and wherein the benzene nucleus R may be substitutedbv substituents of the group consistin ofhalogen, aikyl, the alkoxy, hydroamino, sulfonic acid and carboxylic acid groups, and atleast equimolecular quantity of a water-soluble sulfite, such as sodium bisulfite, and an about equimolecular quantity of general formula:

z@o-a k ooom wherein one 2 stands for an amino group and the other 2 stands for hydrogen, R may be substituted by any s'ubstituents, .allt mean ing analkylene group andR ihydrogen, al-

kyl, or an'alkali metal.

The process is carried out betweenabout manufacture. of dyestuffs.

a compound of the 80C. and the boiling point oi": the reaction mixture and is complete when the starting organic compounds can no more be detected,"

say after several hours. Instead of working- J 55 V with-a mixture of: a B-naphthol or a B-naph-- thyl-amine, a watersoluble sulfite andg'an.

amino phenoxy fatty acid or a salt thereohfi" Our new compounds areg'enerally color-g lesscrystalline substances; soluble in aqueous alkalies from which solutions they are re precipitated by the addition of anaci'd and arevaluable intermediate products in thei The invention is illustrated by the follow ing examples, without being restricted thereto: I

Example 1.17.2 parts by Weight .of- 2 naphthol-3-carb0xylic, acid are dissolved. in 300 parts of water with the addition ofthe quantity of sodium carbonate necessary for neutralization, then mixed with avs olution of i 19.7 parts byweightj of sodium 4- amin o-f phenoxy acetate in 200 parts of water "and heated on the bOilingwaterbath with stir ring with 800 partsby weighty-of sodium bi sulfitesolutiojn (440%). After a -short time" ayigorous evolution of carbon dioxide begins in consequence of thesplitting ofi vof the car boxylicacidjgroup from the nucleus, Heat mg is continued for 8 hours, when the sulturous'acid is boiledoif in'the customary separates, contaminated with a little ele h- ,2-naphthyl t-amin ophenoxy c thol. On recrystallizin for example from etherfth 2'rnaphthylA-amino-phenoxy acetic acid is obtained in the form ofa lwhite crystalline powder, which dissolves readily inalkalies,inelts,at 156? and couples with diazotized 4-nitraniline-2-sulfonic acid inthe presence of acetic acid to form a bluish-violet -dyestuflic 011 using 2-naphthol-6-carboxylic acid in- V, stead of the 2-naphthol-3-carboxylic.acid an exactly analogous process yields 6-carboxy- 2 -naphthyl-4-aminophenoxy acetic acid, and I 1 when instead of the naphtholcarboxylic acids noxy acetic acid is a greyishrgreen crystalline v powder soluble 1n dllute alkalles from which the naphthylamino carboxylic acids are em-' ployed the same end products are obtained.

The 6' carboxy-Q naphthyll amlnophesolution it is precipitated by the addition of acids. In a mineral acid emulsion it can be combined with diazotized l-n1tran1l1ne-2- sulfonic acid giving a difiicultly soluble bluea i slightly colored nitroso compound.

' um 2 naphthol-7-sulionate are dissolved in violet dye. NVith nitrous acid it gives a Ewample Z.2 l.6 parts by weight of sodi- 500 parts of water with 19.7parts by weight 1 of sodium l aminophenoxy'acetate andboiled for 20hours with stirring under a reflux 0011 .25

denser with? 00 parts by weight of a sodium f bisulfite solution (4 0%); Thereafter hydrochloric acidis employed for rendering I I strongly acid to Congo red in the customary I so manner and the sulfurous acid isboiled off.

On cooling theT-sulfo-Z'-naphthyl-4-a1ninophenoxy acetic acidof the'formula Nng-o one-ooon v separates'out" asa finecry'sta'lline powder.

' Theyield is almost theoretical and the final 1 d 'gous manner onfstarting from *2-naphthol- V or; "2 na'phthy1amine-5.7 -disulfonic acid or product is'of great :purity. V I r The process proceeds in an exactly. analo from 2-naphthol-5-r, 6-,"or 8-mono-sulfonic' acid or'from Q-naphthyIamine-d, 6-, 7- or 8-lmoi1osulfonic acid instead of from 2 naphthol-7-sulfonic "acid; Alternatively the sul furous acid compound of the fl-naphthol sulfonic'acid can be first produced in the cusf tomary. manner and this then caused to re- The 7"-sulfo-2-naphthyll-aminophenoxy act with the amino-phenoxy acetic acids.

acetic acid and its sodiumsalt are easily solv 'ub-le in water and are precipitatedfrom the aqueoussolution by the addition of common salt. Combined with l nltranihne-2-sulfomc' acid in an ac dsolution a violet dye results.

I 'VVith nitrous acid a yellowish nitroso compoundis obtained. The 5), 6-,or 8 -sulfo- 2u aphthyl-L or V 3 amino-phenoxy acetic 6 above mentioned 'Zsul io-2-naphthyl-4;-ami- 1 'nophenoxy acetic acid; 7 7

acids have quite similar propertiesrto the I EwampZe'3r-26l parts by weight of sod i 'g"um 2;8 amino-naphthol-6-sulfonate are dis. solved in 500 parts of .watergwith 19.7 parts excess hydrochloric acid and sodium chl'O-1 ride added tothe liquor. On cooling the 8 noxy acetic'acid of the formula;

Hogsseparates out as a sandy powder.

On using 2.8-dihydroxynaphthalene6-sul-" tonic acid instead of the QB-aminonaph thOl-G-sulfonic, acid the same ultimate product isiobtained.

When startingirom 1.6-a'minonaphthol-3:

sulfonic acid the; same methodoi" working yields 5-amino-7-sulf phenoxy acetic acid The 5-amino-7-sulfo-2 -naphthyll ami nophenoxy acetic'acid is a greyish crystalline powder soluble in dilute alkalies. By treatment with nitrous acid'an easily soluble yellow nitroso-diazo compound is obtained.

Combined with diazotized t-nitraniline-Q- sulfonic acid in a weakly mineral acid solu 'tion a bluish-violetdye is obtained.

Example 4.26.2' parts by weight of sodium, 2.5-dihydroxynaphthalene-7-sulfonate are dissolved in 100yparts of water with 19.7

P y Weight f HmaminophenOXy acetate-and boiled'for l o' hours with stirring with SOOparts by weight of sodium bisulfi te. it

After: cooling completely solution (4.0,

the solution is fil ered from theseparatedpre- 'cipitate, After boiling; with hydrochloric acid only very little can be separated from the filtrate. By far the g'reater'p'art of the reaction product isfoun'd' in the residue left on filtration, which ismade into a paste with a little water and heatedwith a1 littlehydm chloric acid to remove any. sulfurousacid still present. After cooling andfiltering the noxy acetic acid of theiormula:

' 1 o-cnrcoon is obtained as a white powder, of great purity and inabout 80% of the calculated yield.

The new compound, infasolution weakly acid to congo' red, coupleswith diazoti'zed 4-ni traniline-2-sulfonic acid to a bluish-violet dyestuff. With nitrous acid it forms a ni-' troso Compound, which on pouring into sodium carbonate solution gives a pale yellow coloration; 4.

On using the l-aminophenoxy acetic acid ethylester instead of the 4-aminophenoxy acetic acid and saponifying the ester the same endproduct is obtained. By replacing the 4-aminophenoxy acetic acid by the l -amino- Q-methylphenoxy acetic acid the same process yields 7 -sulfo-5-hydroxy-2f -naphthyl- 4 v-amino-2-methylphenoxy acetic acid. On starting from l-amino- Q-chlorophenoxy ace-f tic acid (prepared by the interaction of the sodium salt of the corresponding nitrophenol with monochloroacetic' acid and subsequent reduction with iron and aceticacid) there is obtained 7 "-sulfo-5 -hyd'roxy-2-naphthyl-4- amino-Q-chloro-pherioxy acetic acid. All

,- these compounds possess essentially the same droxy-2-naphthyl-4=-aminoproperties and show a similar chemical be haviour to the products described, above.

, Finally on using 4-amino-phenoxy-B-propionic acid there is obtained 7-sulfo-5'-hy- (,8 phenoxypropionic acid). When employing isomeric aminophenoxy acetic acids the isomeric hydroxy sulfonaphthylarnino phenoxy acetic just as smoothly as in the um 2.6 diaminonaphthalene-8-sulfonate are dissolved in '100 parts of water with 19.7

parts by weight of sodium 4-aminophenoxy acetate and boiled for 20 hours with stirring under a reflux condenser with 800 parts by weight of sodium bisulfite solution (40%).

The solution'is then rendered strongly acid to Congo red with concentrated hydrochloric acid and the sulfurous acid boiled off. On

cooling the 6-amino-8-sulfo-2'-naphthyl 4c-.

aminophenoxy acetic acid of the formula:

Nn- 3+o cflrooon separates as a fine crystalline precipitate.

We claim: 1. The process which comprises causing a compound of the general formula wherein a: stands for an amino or a hydroxy group, the ys stand for hydrogemone of which may be substituted by a carboxylic acid group, an at least equimolecular quantity of awatersoluble sulfite and an about equimolec ular quantity of acompound of the general formula; vi

V o ikwooml wherein one 2 standsforan amino group; and the other a standsfor hydrogen, alk :meaning an alkylene group,R :,stands for 'hydrogen, alkyl or an alkali metal,'th'e nuclei B and R of the components maybe substituted by subsfituentsgof the group consisting ofhalo-j gen, alkyl, the alkoxy, hydroxy, amino,.sulifonicacid and carboxylic acid groups,to reactupon each other in aqueous solutlon or suspension at a temperature between about C. and the boiling point of the reaction mixture for severalhours. 2. The process wh ch. com frlses compound; ofthe general formula:

wherein in stands for an amino or ahydroxy? group, the-ys standfor. hydrogen lone-jof Which-may be substituted by carboxylic' acid group, an at least equimolecular quan-'- tity of sodiumf bisulfite and an about "equi-i molecular quantity- 0f ajfcompound of the generalfformulaz Y I wherein one 2 stands for an aminogroup and the other-z stands for hydrogen, R5 stands for hydrogen, alkyl or, an alkali metal," the nuclei B and R5 of the, components may ,be

substituted by substituents-of the group consisting of halogen, alkyl, the; "alkoxy, by

droxy', amino, sulfonic acid and carboxylic e d o pst' red n t he injaqw one solution vor suspension at aftemperatur'e between'ab'out 8.0? C. and: the; boiling point ofthe reaction mixtujreforjseveral' hour s. 4

3. The process which comprises causing a compound of the general formula:

an at least equiniolecularquantity sodium bisulfite and anaboutequimolecular'q'uantity of, acompound ofthe general formula; "7

wherein R stands' for" hydrogenor an iiklii metal, the. nuclei. R and: B2. of the compone nts may be substituted by. substituents of the-group consisting of halogen, alkyl, the al-- koxy, hydroxy, amino, sulfonic acid and carboxylic acid groups, to react upon each other in aqueous solution at a temperature'between about'SO C. and the boiling point of the reaction mixture for several hours.

4."The processwhich comprises bo l ng in aqueous solution sodium-2.5-dihydroxynaphtha'lene-lsulfonate, an at least equimolecular quantity of sodium :bisulfite and an about. equimolecular quantity--of sodium paraaminophenoxy acetate for several hours.

5. As new products B-naphthylaminoarylhydroxy fatty acids of the probable general yformula z j yvherein alk stands for: an alkylene group the group NI Ifbeing attached tolthe benzene nucleus R in paraor meta-position 'to the Y hydroxy 'fatt yacid residue, and wherein the V v benz ene'nucle-i R and R may be substituted by substituents ofvthe-group consisting of halogen, alkly, the alkoxy, hydroxy, amino,

sulfonic acid and carboxylic acid groups, be-

' 3O r soluble in aqueous alkalie's from whichsolu- Y 1 i-nggenerally colorless,-crystal1ine substances,

tions they are reprecipitated by the addition of :anacid and being valuable intermediate products in the manufacture of dyestuffs,

, 6. As newproducts B-naphthylaminoarylhydroxy fatty acids of the probable general formula; i I

wherein alk stands for an alkylene and the benzene nuclei R and R5 may vbesubline substances, soluble in aqueous' alkaliesf l i from which solutionsthjey are reprecipitated by the addition of an acid and beingvaluable intermediate products in the manufacture ot dyestuffs.

8. As a new product the B-naphthylaminoi aryl'hydroxy y. flcidi f the probable formula: j v a being a White powder, soluble Waterand being a valuable intermediate manufacture of dyestufis.

product'rin the In testimonyowhereof, We afiix our signa V WINFRID, HENTRIorrj I tures;

" I JOSEF ILGER. a i

RUDOLF VKNOGI-IEJY ,i I

stituted bysubstituentsof the group consistv j ing othalogen, alkyl, the al'koxy, vhydroxy, amino, fsulfonic acid and carboxylic acid groups, being generally colorless crystalline i 'sub'stanciegsoluble in aqueousfalkalies from which solutions; they are repreoipitated by the addition ofanyacid and being valuable intermediate products in the manufacture of hydroxy fatty acids 'of-the probable general formula: a

7. AS new oducts jB-naphthy1 fin6 fy 

